Preparation of oxirane compound from the corresponding olefin via the cyclic carbonate ester

ABSTRACT

are prepared by reacting the corresponding vicinal halohydrin with carbon dioxide in the presence of an amine compound and are decomposed to produce oxirane compounds.   Cyclic carbonate esters having 3 to 31 carbon atoms per molecule of the general formula

[ Dec. 2, 1975 1 PREPARATION OF OXIRANE COMPOUND FROM THE CORRESPONDING OLEFIN VIA THE CYCLIC CARBONATE ESTER [75] Inventor: Yulin Wu, Bartlesville, OK

[73] Assignee: Phillips Petroleum Company,

Bartlesville, Okla.

[22] Filed: June 28, 1974 [211 App]. No.: 484,262

[52] U.S. Cl 260/348 R; 260/340.2; 260/634 [51] Int. Cl. C07D 301/02 [58] Field of Search 260/340.2, 348 R [56] References Cited UNITED STATES PATENTS 2,773,070 12/1956 Lichtenwalter et al 260/340.2 2,773,881 12/1956 Dunn 260/340.2 3,535,341 10/1970 Emmons et al. 260/340.2

FOREIGN PATENTS OR APPLICATIONS 35,311 11/1970 Japan 260/340.2

Germany 260/340.2 Gennany 260/348 R Primary ExaminerN0rma S. Milestone [5 7] ABSTRACT Cyclic carbonate esters having 3 to 31 carbon atoms per molecule of the general formula are prepared by reacting the corresponding vicinal halohydrin with carbon dioxide in the presence of an amine compound and are decomposed to produce oxirane compounds.

9 Claims, N0 Drawings PREPARATION OF OXIRANE COMPOUND FROM THE CORRESPONDING OLEFIN VIA THE CYCLIC CARBONATE ESTER This invention relates to the preparation of cyclic carbonate esters.

Cyclic carbonate esters of vicinal dialcohols are well known in the art. One method for making such esters involves the reaction of the corresponding halohydrin with sodium bicarbonate under pressure of carbon dioxide. This method produces water as a by-product which causes considerable loss of product by hydrolysis to the corresponding diol, from which it is difficult to separate the carbonate ester. Another method for preparing such-cyclic carbonate esters involves the reaction of an alkali metal alkyl carbonate with a halohydrin to form the alkyl hydroxyalkyl carbonate, which undergoes internal ester exchange to form an alkylene carbonate.

It is an object of this invention to provide a novel process for the preparation of cyclic carbonate esters.

It is another object of this invention to provide an improved process for the preparation of cyclic carbonate esters from olefins.

Other objects, aspects and advantages of this invention will become apparent to those skilled in the art upon reading the specification and appended claims.

In accordance with this invention, it has been discovered that cyclic carbonate esters having from 3 to 31 carbon atoms per molecule of the general formula wherein each R and R is individually selected from the group consisting of hydrogen and hydrocarbyl radical groups, as hereinafter defined, having from 1 to carbon atoms, and wherein both R radicals can represent a divalent aliphatic hydrocarbon radical which together with the carbon atoms to which the carbonate group is attached can form a cycloaliphatic ring, are prepared by reacting carbon dioxide with the corresponding vicinal halohydrin having from 2 to 30 carbon atoms per molecule of the general formula drins is the reaction of a suitable olefin with oxygen in the presence of an iron halide and a copper halide. For example, a mixture of l-chloro-2-propanol and 2- chloro-l-propanol is prepared by the reaction of propylene'with oxygen in the presence of ferric chloride hexahydrate and cupric chloride or cuprous chloride, with ferric oxide as a coproduct of this reaction.

Examples of vicinal halohydrins suitable for use in the process of this invention include 2-chloroethanol, l-chloro-Z-propanol, 2chlorol -propanol, 2-chlorol octanol, l-chloro-2-octanol, 2-chlorocyclohexanol, 2- chlorol ,2-dipenylethanol, 2-bromo-l ,2-diphenylethanol, 1-chloro-2-methyl-2-propanol, 2-chloro-3-phenyl-l-propanol, 2-chlorocyclopentanol, 2-bromocyclooctanol, l-bromo-2-hexanol, 2-bromol -hexanol, 2-bromoethanol, 2-iodoethanol, l-bromo-Z-propanol, 2-bromo-l-propanol, 2-bromocyclohexanol, 2-bromo- 4-tert-butylcyclohexanol, 2-bromo-2-methylcyclohexanol, 2-iodocyclohexanol, 2-chloro-l-octadecanol, lchloro-2-octadecanol, 3-chloro-2,3-dimethyl-2- butanol, and the like. Mixtures of the above compounds can be employed if desired and is especially useful when isomeric compounds are employed, e.g., l-chloro-2-propanol and 2-chloro-1-propanol.

The amines suitable for use in the process of this invention are selected from the group consisting of ammonia and organic amino compounds having from 1 to about 30 carbon atoms and from 1 to about 5 amino groups per molecule, wherein the amino groups can be primary (NH secondary NH), tertiary or mixtures thereof. It is preferred that the organic amino compounds used in the practice of this invention contain only carbon, hydrogen and nitrogen; however, substituents which do not interfere with the reaction of carbon dioxide with the above-described halohydrins can be present in the amine compound, as for example, ethereal oxygen.

Examples of suitable amine compounds include ammonia, methylamine, ethylamine, dodecylamine, octadecylamine, octadecylamine, diethylamine, triethylamine, di-n-butylamine, cyclohexylamine, aniline, benzylamine, N-methylaniline, N,N,N,- N'-tetramethylethylenediamine, 1,6-diaminohexane, tetraethylenepentamine, and the like.

In a presently preferred embodiment of this invention, the amine is a saturated aliphatic amine having from 1 to 10 carbon atoms per molecule. Examples of presently preferred amine compounds include diethylamine, triethylamine, di-n-butylamine, di-n-pentylamine and the like.

The amount of amine employed in the process of this invention is generally from about 0.1 to about 4 gram equivalents of amino group per gram mol of vicinal halohydrin. It will be appreciated-that an amine compound having 1 amino group per molecule has 1 gram equivalent of amino group per gram mol of said compound; an amine compound having 2 amino groups per molecule has 2 gram equivalents of amino group per gram mol of compound, and so forth.

In a presently preferred embodiment the amount of amine compound employed in the process of this invention is in the range of 0.9 to 1.5 gram equivalents of amino group per gram mol of vicinal halohydrin.

hexylamine,

3 Reaction conditions vary according to starting materials. In general, the process is conducted at a temperature which will allow for formation of the cyclic carbonate ester without undesirable side reactions, for a 4 posed to produce an oxirane compound and carbon dioxide. The carbon dioxide produced in the third step can be recycled as a reactant to the second step. It will be appreciated that material quantities, reaction conditime sufficient to provide essentially complete conver- 5 tions and recovery methods are within the skill of one sion. in this art.

The temperature employed in the process of this in- The following examples illustrate the invention. vention can be in the range of 0 to 200C. In a presently preferred embodiment, the temperature is in the EXAMPLE I range of 40 to 140C. Two runs were carried out in which 25.5 g (0.316 Carbon dioxide pressure can be in the range of 0 to mol) 2-chloro-l-ethanol was reacted with 22 g (0.301 10,000 psig. A pressure in the range of 50 to 500 psig mol) diethylamine and C0 (400 psig) in the presence is presently preferred. of 60 ml benzene. Two different reaction temperatures The process of this invention can be carried out in were employed. The reaction time in each run was 5 the presence or absence of an inert diluent. It is preshours. Each run was conducted by charging the halohyently preferred that an inert diluent which is a good 501- drin, amine and benzene to an autoclave, stirring and vent for carbon dioxide be employed. Examples of suitheating to the desired temperature and then charging able diluents include methanol, acetone, toluene, benthe carbon dioxide. At the end of the reaction period zene and the like. the reaction mixture was filtered. The recovered solid The cyclic carbonate ester prepared according to the material was dried and the filtrate was analyzed by gasprocess of this invention can be recovered from the reliquid chromatography (GLC). Results of the above action mixture by conventional methods. The amine runs are shown in Table I below. hydrohalide salt produced as a coproduct of the reac- Table 1 tion is generally insoluble in the reaction mixture; it can I Halohydrin be removed by filtration. The filtrate can be fraction Run Temp" Conversion Selectivity, Amine Sam", ally distilled to recover the carbonate ester. N0, to Carbonate g (mol) The carbonate esters prepared according to this ml 7O 9O 90 23.9 (0118) ventlon are useful as solvents for a variety of processes, 2 90 3g 91 2595 (0,236) extraction of Sulfur Compounds from petroleum frac- "D' th I mine h hloride filter d from the reaction mixture and dried tions and the like. These carbonate esters can also be ya y we e decomposed to produce oxirane compounds having the general f l The results shown in Table I show the high degree of conversion of 2-chlorol-ethanol to ethylene carbonate according to this invention. It can be further seen that i about 75 mol percent of the amine compound could be R R recovered from the mixture as the hydrochloride salt 0 simply by filtering the reaction mixture to recover the solid product.

wherein R and R are as defined hereinbefore. The oxi- 40 EXAMPLE II :32; g? i ggg g g g fi Two runs were carried out in which diethylamine and p y y a mixture of l-chloro-2-propanol (78.6%) and 2- The process of this invention is well adapted for use in a three-ste c clic rocess for the roduction of an chloro'l'pmpanol (214%) were charged to reactors oxirane com g g frog an Olefin AS first Ste a Suit in amounts given in Table II below. The reactors were charged with carbon dioxide to about 400 psig, then able olefin is reacted with oxygen in the presence of an v heated to the temperatures given in the following table iron halide to produce a vicinal halohydrin. The cofor the tlmes given. At the end of each reaction period, product of this reaction IS an iron oxide. In the second h t l d d d h H step the vicinal halohydrin is then reacted with carbon t e reac or was C00 6 vente an t e contents dioxide in the resence of an amine to 'rovide a 0 die tered. The filtrates were analyzed by GLC. The results p p r y of these runs are shown in Table H below.

Table II Halo- Selechydrin tivity Halo- Conto Car- Run hydrin, Et NH, Temp. Time, version, bonate, No. g (mol) g (mol) C. Hrs.

carbonate ester and an amine hydrohalide salt. The iron oxide produced in the first reaction can be reacted with the amine hydrohalide salt to regenerate the iron In run 3, analysis of the filtrate further showed that halide and the amine compound. The latter reaction the conversion of l-chloro-2-propanol was 99% while can be accomplished by admixing the iron oxide and the conversion of 2-chloro-l-propanol was 50.5% the amine salt, heating the admixture to about 250C 65 under the reaction conditions given above.

and separately recovering therefrom, by conventional methods, the iron halide and the amine compound. In the third step, the cyclic carbonate ester can be decom- The above results indicate the excellent selective conversion of halohydrin to carbonate esters in the absence of a diluent according to this invention.

L ,EXAMPLE'Iii Two runs were carried out inwh-icha mixture'of lchloro-2-propanol (78.6%) and 2 -chlo ro-1-,pr.opanol cthylamine, wcre' collected-in 'a'dr'y icej't'ra'p r Reasonable variations and: modificati'bns of this" invention will be "apparentto those's'kiild in the art in aboiit 66165266,; of the dcciiniposition prdductfdi-,

1.6 g (0.01 mole) of ferric oxide were ground and charged to a two-neck flask equipped with stirrer and condenser. The mixture was heated to about 235C for (21.4%) was charged togetherwith triethy-lamine-and' 5 view. of this disclosure -Suchvariations and 'modi fi tia benzene to a reaction vessel inlamounts shown. below-,- tib'n's are within the' 's cojpe and spiiif'of the disclosu're. Thereactorvessels were pressurized with carb,on diox-. What"is'clairned is: ide as shown in the following table. The reactors were 1; Aprocessfor the prepai'a'ti'bri of'ah oxir'ane cdn'ithen heated-at 70C fori hours. At the end of the reac- I pound frprn the corresponding olefin which comprises tion periodfthje reactor ,was cooled, ven ted an d the the's t'e'ps oi. H contents filtered. The filtrate was analyzed. GLC. a. forming a 'vicinal halohydrin having from 2' to 30 Conversion and selectivity data ar'e given in Table 111' carbon atom s'per molecule' of'the formula b o v s I Table 111 Halo- Selechydrin tivity Halo- .Conto Car- Run hydrin, Et N, Benzene, CO2, version, bonate, N0. g (mol) g (mol) ml. psig 5 10(O.l06) 11(0.109) 200 67.5 81 6 29(0.212) 21.4(0.2l2) 40 400 87 95 In run 5, the analysis of the filtrate further showed that the conversion of 1-chl0ro-2-propanol was 83% R R while the conversion of 2-chloro-1-propan0l was only H X i 5.5% under the reaction conditions of thisrun. In run 6,

conversion of 1-chloro-2-prOPan Was 98% and wherein each R and R is individually selected from of was under the 30 the group consisting of hydrogen and hydrocarbyl macho condmons f f above" radical groups having from 1 to 10 carbon atoms The above results indicate the excellent convers on and wherein both groups in Said halohydrin can ndiflselsctwlty afforded s E mvemfon represent a divalent aliphatic hydrocarbon radical and indicate further the differing reactivities the is0- which together with thercarbon atoms to which the rnerrc halohydrins at different reaction conditions. 5 and the groups are attached can form a EXAMPLE v cycloal-iphatic ring, and X is selected from the t group consisting of chlorine, bromine and iodine, W were earned out m whlch 10 g (0106 mol) byreacting the corresponding olefin of the formula of a mixture of 1-chloro-2-propanol. (78.6%) and 2- D .chloro-l-propanol (21.4%),7.82 g (0.107 mol) of di- 40 I H .ethylamineand 20 ml. of benzene were charged to a s 200 mLaerosol compatibility bottle. The reactors were i l charged with carbon dioxide to about 100 psig, then R R immersed in a constant temperature oil bath for 4-5 v hours reaction period for each run. At the end of each wherein R and a as d fi 'd' b with reaction period, the reactor was cooled, vented and the gen in the presence of an iron halide and a copper contentsfilteredh dethylafmme halide, under reaction conditions, wherein there is drochlollde, was washed with benzene and dried under formed as a copmduct an iron oxide; vacuum at 100C overnight. The filtrate was analyzed separately recovering from Step (a), Said vicinal by GLC. The results of these runs are shown in Table halohydrin and Said iron oxide; below c. reacting said vicinal halohydrin, an amine and car- T bl [V bon dioxide, under reaction conditions, to form a Run Tcrnp., Halohydrin Selectivity to Amine Salt cyclic carbonate ester having from 3 to carbon No. "C Conversion, Carbonate, 7: g (mol) atoms P molecule of the formula 7 50 61.2 79 6.48 (0.059) i 8 70 74.5 86.5 7.88 (0.072) R R R i R The above results illustrate the desired conversion 4) with high selectivity of the halohydrin to the carbonate .ester at relatively low carbon dioxide pressure and temg perature.

EXAMPLE V wherein R and R are as defined above, wherein 6.6 g (0.06 mole) of diethylamine hydrochloride and there is formed as a coproduct an amine hydrohalide; i

d. separately recovering from step (c) said ester and said amine hydrohalide;

from step (b) is reacted with said amine hydrohalide from step (d) to regenerate said iron halide and said amine.

3. The process of claim 2 wherein said irdn halide is T g d to the process of claim 2, Step 4. The process of claim 2' wherein said amine is passed to the process of claim 2, step (c).

5. The process of claim 1 wherein said carbon dioxide recovered in step (f) is passed to step (c).

6. The process of claim 1 wherein said amine is selected from the group consisting of ammonia and organic amino compounds having from 1 to 30 carbon atoms and from I to 5 aminogroups per molecule.

7. The process of claim 6 wherein said amine is a saturated aliphatic amine having from 1 to 10 carbon atoms per molecule.

8. The process of claim 1 wherein said amine is employed in step (c) in an amount ranging from about 0.9 to about L5 gram equivalents of amino group per gram mol of said vicinal halohydrin.

9. The process of claim 1 wherein said olefin is propylene and said oxirane is propylene oxide.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,923,8h2 DATED December 2, 1975 lN\/ ENTOR(S) Yulin Wu It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 7, line 11, claim 3, "claim 2" should be claim 1 Signed and Scaled this sixth Day of April1976 [SEAL] A ttes r.-

RUTH C. MASON Atresling Ojficer C. MARSHALL DANN Commissioner oj'PaIenIs and Trademarks 

1. A PROCESS FOR THE PREPARATIONOF AN OXIRANE COMPOUND FROM THE CORRESPONDING OLEFIN WHICH COMPRISES THE STEPS OF: A. FORMING A VICINAL HALOHYDRIN HAVING FROM 2 TO 30 CARBON ATOMS PER MOLECULE OF THE FORMULA
 2. The process of claim 1 wherein said iron oxide from step (b) is reacted with said amine hydrohalide from step (d) to regenerate said iron halide and said amine.
 3. The process of claim 2 wherein said iron halide is passed to the process of claim 2, step (a).
 4. The process of claim 2 wherein said amine is passed to the process of claim 2, step (c).
 5. The process of claim 1 wherein said carbon dioxide recovered in step (f) is passed to step (c).
 6. The process of claim 1 wherein said amine is selected from the group consisting of ammonia and organic amino compounds having from 1 to 30 carbon atoms and from 1 to 5 amino groups per molecule.
 7. The process of claim 6 wherein said amine iS a saturated aliphatic amine having from 1 to 10 carbon atoms per molecule.
 8. The process of claim 1 wherein said amine is employed in step (c) in an amount ranging from about 0.9 to about 1.5 gram equivalents of amino group per gram mol of said vicinal halohydrin.
 9. The process of claim 1 wherein said olefin is propylene and said oxirane is propylene oxide. 